The x‐rayKabsorption spectra of the constituent atoms in fcc solid solutions of Mn in Cu, Ni, Co, and Fe show systematic changes taking place with increasing manganese concentration which it is not possible to explain in terms of the rigid‐band model for alloys. A decline in the initial rise in absorption with increasing Mn content is observed for all absorption edges except for Mn in Mn&sngbnd;Fe solid solutions, in which case an increase takes place. A tentative explanation, based on hybridization of the outer states upon alloying, is proposed for Mn&sngbnd;Cu and Mn&sngbnd;Ni alloys.